US5746778A - Wood stain containing a stabilizing agent - Google Patents
Wood stain containing a stabilizing agent Download PDFInfo
- Publication number
- US5746778A US5746778A US08/652,309 US65230996A US5746778A US 5746778 A US5746778 A US 5746778A US 65230996 A US65230996 A US 65230996A US 5746778 A US5746778 A US 5746778A
- Authority
- US
- United States
- Prior art keywords
- acid
- wood
- water
- stain
- comprised
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000002023 wood Substances 0.000 title claims abstract description 83
- 239000003381 stabilizer Substances 0.000 title claims abstract description 30
- 238000010186 staining Methods 0.000 claims abstract description 58
- 239000000975 dye Substances 0.000 claims abstract description 44
- 239000008139 complexing agent Substances 0.000 claims abstract description 30
- 239000000872 buffer Substances 0.000 claims abstract description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 29
- -1 iron ion Chemical class 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052742 iron Inorganic materials 0.000 claims abstract description 28
- 239000001003 triarylmethane dye Substances 0.000 claims abstract description 9
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 30
- 235000012756 tartrazine Nutrition 0.000 claims description 29
- 239000004149 tartrazine Substances 0.000 claims description 29
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 claims description 27
- HMEKVHWROSNWPD-UHFFFAOYSA-N Erioglaucine A Chemical compound [NH4+].[NH4+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 HMEKVHWROSNWPD-UHFFFAOYSA-N 0.000 claims description 23
- 235000012745 brilliant blue FCF Nutrition 0.000 claims description 23
- UJMBCXLDXJUMFB-GLCFPVLVSA-K tartrazine Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C1=NN(C=2C=CC(=CC=2)S([O-])(=O)=O)C(=O)C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 UJMBCXLDXJUMFB-GLCFPVLVSA-K 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 14
- UJMBCXLDXJUMFB-UHFFFAOYSA-K trisodium;5-oxo-1-(4-sulfonatophenyl)-4-[(4-sulfonatophenyl)diazenyl]-4h-pyrazole-3-carboxylate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C1=NN(C=2C=CC(=CC=2)S([O-])(=O)=O)C(=O)C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 UJMBCXLDXJUMFB-UHFFFAOYSA-K 0.000 claims description 14
- 239000004161 brilliant blue FCF Substances 0.000 claims description 13
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 12
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 12
- 235000012731 ponceau 4R Nutrition 0.000 claims description 12
- 239000003755 preservative agent Substances 0.000 claims description 11
- 239000000080 wetting agent Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 9
- VXIVSQZSERGHQP-UHFFFAOYSA-N chloroacetamide Chemical compound NC(=O)CCl VXIVSQZSERGHQP-UHFFFAOYSA-N 0.000 claims description 8
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 8
- 239000004299 sodium benzoate Substances 0.000 claims description 8
- 235000010234 sodium benzoate Nutrition 0.000 claims description 8
- 235000012709 brilliant black BN Nutrition 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- JGUQDUKBUKFFRO-GGWOSOGESA-N (NE)-N-[(3E)-3-hydroxyiminobutan-2-ylidene]hydroxylamine Chemical compound O\N=C(/C)\C(\C)=N\O JGUQDUKBUKFFRO-GGWOSOGESA-N 0.000 claims description 5
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
- 229940053200 antiepileptics fatty acid derivative Drugs 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 239000001632 sodium acetate Substances 0.000 claims description 5
- 235000017281 sodium acetate Nutrition 0.000 claims description 5
- GMMAPXRGRVJYJY-UHFFFAOYSA-J tetrasodium 4-acetamido-5-hydroxy-6-[[7-sulfonato-4-[(4-sulfonatophenyl)diazenyl]naphthalen-1-yl]diazenyl]naphthalene-1,7-disulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].OC1=C2C(NC(=O)C)=CC=C(S([O-])(=O)=O)C2=CC(S([O-])(=O)=O)=C1N=NC(C1=CC(=CC=C11)S([O-])(=O)=O)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 GMMAPXRGRVJYJY-UHFFFAOYSA-J 0.000 claims description 5
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 claims description 5
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 4
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical class OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical class OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 229960001484 edetic acid Drugs 0.000 claims description 3
- CUXQLKLUPGTTKL-UHFFFAOYSA-M microcosmic salt Chemical compound [NH4+].[Na+].OP([O-])([O-])=O CUXQLKLUPGTTKL-UHFFFAOYSA-M 0.000 claims description 3
- 235000012736 patent blue V Nutrition 0.000 claims description 3
- 229960003330 pentetic acid Drugs 0.000 claims description 3
- 235000021317 phosphate Nutrition 0.000 claims description 3
- 150000003013 phosphoric acid derivatives Chemical group 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 2
- 230000002335 preservative effect Effects 0.000 claims 5
- IPBVNPXQWQGGJP-UHFFFAOYSA-N phenyl acetate Chemical group CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 17
- 229910000831 Steel Inorganic materials 0.000 abstract description 14
- 239000010959 steel Substances 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 13
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 10
- 230000000694 effects Effects 0.000 description 9
- 230000008859 change Effects 0.000 description 7
- 238000002845 discoloration Methods 0.000 description 6
- 230000006735 deficit Effects 0.000 description 5
- 230000001771 impaired effect Effects 0.000 description 5
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 4
- 239000001043 yellow dye Substances 0.000 description 4
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 3
- 239000000980 acid dye Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000000149 penetrating effect Effects 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- XFLNVMPCPRLYBE-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;tetrahydrate Chemical compound O.O.O.O.[Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O XFLNVMPCPRLYBE-UHFFFAOYSA-J 0.000 description 3
- 240000000896 Dyera costulata Species 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000000987 azo dye Substances 0.000 description 2
- 239000012928 buffer substance Substances 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 2
- 241000218645 Cedrus Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000007903 penetration ability Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- KOPFEFZSAMLEHK-UHFFFAOYSA-N pyrazolecarboxylic acid Natural products OC(=O)C=1C=CNN=1 KOPFEFZSAMLEHK-UHFFFAOYSA-N 0.000 description 1
- 239000001044 red dye Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000007447 staining method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D15/00—Woodstains
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/16—Inorganic impregnating agents
- B27K3/20—Compounds of alkali metals or ammonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/34—Organic impregnating agents
- B27K3/36—Aliphatic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/34—Organic impregnating agents
- B27K3/38—Aromatic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/52—Impregnating agents containing mixtures of inorganic and organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
- B27K5/02—Staining or dyeing wood; Bleaching wood
Definitions
- This invention relates to a water-based stain for staining wood containing at least one dye, such as azo, diazo and triarylmethane dyes, and to a method for staining wood.
- the present invention relates to use of a stabilizing agent which may be a buffer and/or a complexing agent and which is effective to reduce the concentration of free iron ions in the stain from contact with an autoclave composed of non-rust-resistant steel, and thereby reduce coloration impairment of the stain.
- Wood stains are known, for example, from the furniture industry and are used for staining the surface of a piece of furniture while preserving its natural grain if possible.
- the surfaces of the pieces of furniture are treated with the stain by, for example, painting or spraying, and any other method know in the art. In such treatment processes the stain penetrates the wood surface only slightly. However, this is often not sufficient for achieving the desired staining of the wood surface.
- staining that penetrates deeper into or even entirely through the wood. The latter is the case in connection with the manufacture of lead pencils and colored pencils wherein the body of wood enclosing the lead of the pencil is intended to have a continuously uniform coloration.
- a further example of applications where penetrating staining of wood is desired is for wood blanks which are intended to be worked later, for example, by cutting or sawing, without the plain, unstained wood appearing at the worked places.
- Such staining processes are usually performed in autoclaves.
- small pieces of wood e.g., wood blanks in the form of small boards in the case of lead pencil or colored pencil manufacture, are placed into an autoclave and dipped into a colored stain. Then the autoclave is closed and the staining or penetrating staining is started by means of temperature and pressure increases as is well known in the art.
- penetrating staining can take several hours or even several days.
- the dyes used can naturally be from a very broad spectrum of different dye types. However, as a rule two groups of dyes are used for staining wood, namely, acid dyes, which are also called anionic dyes, and basic or cationic dyes.
- the color change effect occurs in particular with azo- and diazo-dyes, but in a weakened form, also with triarylmethane dyes.
- acid dyes are used in a neutral to alkaline environment.
- the pH value of the stain typically has been lowered to a varying degree into the acid range, depending on the type of wood used.
- organic acids are contained in the wood which cause an increase in the H 3 O+ ion concentration.
- this effect cannot be or at least cannot be totally responsible for the observed color changes, since generally no color changes were observed in connection with autoclaves of special steel in spite of the lowering of the pH values.
- a wood stain which is water-based and which is suitable for staining wood, comprising: water; at least one dye selected from the group consisting of azo, diazo and triarylmethane dyes; and a stabilizing agent which is effective to reduce free iron ion concentration.
- the wood stain has a pH and the stabilizing agent comprises at least one buffer effective to maintain the pH of the wood stain at greater than 7.0.
- the at least one buffer may be at least one inorganic salt which is water-soluble.
- the stabilizing agent may alternatively or additionally comprise at least one complexing agent which forms a complex with iron ions.
- the wood stain may additionally comprise at least one auxiliary agent selected from the group consisting of wetting agents, water-soluble wax dispersions, water-soluble fatty acid derivatives, and preserving agents.
- the present invention additionally provides a method for staining wood, comprising: placing the wood into an autoclave composed of non-rust-resistant steel; submerging the wood in a wood stain according to the invention; and staining the wood under pressure and temperature conditions effective therefor.
- the present invention additionally contemplates reducing coloration impairment of dyes contained in wood stain during staining of wood in an autoclave composed of non-rust-resistant steel, the wood stain being comprised of water and at least one dye selected from the group consisting of azo, diazo and triarylmethane dyes, by incorporating into the wood stain a stabilizing agent according to the invention which is effective to reduce free iron ion concentration in the wood stain when in contact with the autoclave.
- the stain of the invention contains a stabilizer which reduces the amount of iron from the autoclave which would otherwise solubilize as iron ions into the stain. It was surprisingly shown that, by means of this, the previously observed color changes no longer occur or occur only after considerably longer treatment periods.
- the concentration of the iron ions which move into the dye solution is reduced or kept small by the stabilization agent added in accordance with the invention and, therefore, the effect on the chromophoric groups of the dyes is reduced.
- the effect of the iron ions on the dye can be interpreted in such a way that the iron ions cooperate with the ⁇ -electron systems of the dye as does a Lewis acid and, in the process, changes its light adsorption properties. It therefore appears that the concentration of free iron ions plays a decisive role in the generation of the color change effect. In the neutral or alkaline environment usually present in the mentioned dye-containing stains these would overwhelmingly be Fe-III-ions.
- the stabilizing agent may be a buffer substance which maintains the pH value of the stain at a level which is greater than 7.0. Then, little or no concentration of Fe-II and Fe-III ions can even be created in this pH range, since the iron ions are precipitated as iron hydroxide.
- the buffer which preferably is a water-soluble inorganic salt, counteracts a lowering of the pH by organic acids present in the wood. Substances are advantageously employed as buffers which neither enter into an interaction with the wood to be dyed nor with the dye employed.
- Buffer substances such as acetates and carbonates of ammonium, potassium and sodium, as well as ammonium hydrogen phosphate, secondary and tertiary phosphates of potassium and sodium or ammonium sodium hydrogen phosphate should be mentioned here by way of example but not limitation.
- organic buffer substances can also be used, for example, sodium acetate.
- the iron ions can also be made innocuous in that they may be masked with the aid of a complexing agent.
- the formation of a concentration of iron ions per se is not prevented by this, but they are no longer free ions, i.e., they are captured by the ligands of the complex-forming substance and are therefore shielded so to speak.
- their property as a Lewis acid in respect to the ⁇ electrons of the dye cannot be brought to bear.
- the following substances may be used as complexing agents and are given by way of example but not limitation: diacetyldioxime, 1,10-phenanthroline, terpyridine and water-soluble salts of ethylene-diaminetetraacetic acid, diethylenetriamine pentaacetic acid or 1,2-cyclohexylinedinitrilotetraacetic acid.
- the stabilizing agent can also contain a buffer substance, as well as a complexing agent. It has been surprisingly shown that a stabilization of the stain, which exceeds the extent of the effects of the individual substances, was achieved by the simultaneous presence of a buffer and a complexing agent as will be discussed further in the following.
- the stain in accordance with the invention can additionally contain the usual additives employed with such stains as is known in the staining art, such as wetting agents, water-soluble wax dispersions, fatty acid derivatives, and preserving agents, without interference with the effect in accordance with the invention.
- the addition of preserving agents, such as fungicides, is indicated, for example, if stained wood blanks are intended to be stored over extended periods of time under humid conditions, such as in the tropics. It is mainly their job to prevent the wood blanks from being affected by fungi.
- Water-soluble wax dispersions or water-soluble fatty acid derivatives are added, for example, if it is intended to produce pencils.
- the mentioned substances are deposited in the hollow or capillary spaces of the wood and make it possible to easily sharpen the pencil made therefrom in that the chips cut from the tip cone of the pencil do not break easily and crumble.
- the surface tension of the main constituent of the stain, water, is reduced by the addition of a wetting agent.
- the penetration ability of the stain into the capillary system of the wood is increased thereby.
- a composition of the wood stain in accordance with the invention in weight-%, comprises from about 1 to about 20% of at least one dye; from about 0.01 to about 5% of at least one wetting agent; from about 0.1 to about 0.5% of at least one preserving agent; from about 1 to about 20% of a stabilizing agent, and remainder water.
- Advantageous formulations for stains in accordance with the invention are given herein in the Examples which follow.
- a laboratory autoclave with a capacity of approximately 5 liters was used for preparing the following exemplary formulations.
- the autoclave was made of ordinary steel, i.e., non-rust-resistant steel. Contact of the stain with the mentioned material was always the case.
- the autoclave was filled with stain at least sufficiently for the wood pieces to be completely covered by the stain.
- the temperature in all cases was 50° C. to 60° C.
- the pH value fell to a level of between 8 and 10. Furthermore, pressure values between 13 and 15 bar were maintained.
- test pieces were taken out and the coloration of the pieces and/or of the rest of the stain remaining in the autoclave was checked. Then fresh, i.e., unstained pieces were inserted and the stain used up in the previous staining process was replenished.
- C.I. 19140 is C 16 H 9 N 4 O 9 S 2 Na 3 which is the trisodium salt of 5-hydrox-1-(4-sulfonatophenyl)-4-(4-sulfonatophenylazo)- pyrazole-3-carboxylic acid.
- C.I. 16255 is C 20 H 11 N 2 O 10 S 3 Na 3 which is the trisodium salt of 7-hydroxy-8-(4-sulfonato-1-naphthylazo)-napthaline-1,3-disulfonic acid.
- C.I. 42090 is C 37 H 34 N 2 O 9 S 3 Na 2 which is the disodium salt of ⁇ - ⁇ 4-(N-ethyl-3-sulfonatobenzylamino)phenyl ⁇ - ⁇ - ⁇ 4-(N-ethyl-3-sulfonatobenzylimino)-cyclohexa-2,5-dienylidene ⁇ -toluene-2-sulfenic acid.
- C.I. 42051 is (C 27 H 31 N 2 O 7 S 2 )CA or C 27 H 31 N 2 O 7 S 2 Na which is either the calcium salt or the sodium salt of 2,4-disulfo-5-hydroxy-4', 4"-bis-(diethylamino)-triphenyl-carbinolanhydride.
- C.I. 28840 is C 28 H 27 N 5 O 14 S 4 Na 4 which is the tetrasodium salt of 4-acetamido-5-hydroxy-6- ⁇ 7-sulfonato-4-(4-sulfonatophenylazo)-1-naphthylazo ⁇ naphtalene-1,7-disulfonic acid.
- the two dyes used in the above two tests are azo dyes, while acid blue 9 is a triarylmethane dye. These dyes belong to the group of acid or anionic dyes.
- the test result in accordance with Example 1 can be interpreted as follows: the azo dyes, i.e., acid yellow 23 and especially acid red 18, are the most sensitive. They are impaired first. Thus, the red tones of the dye mixture are weakened first. The relative proportion of the blue and yellow dye accordingly increases, which results in the observed green coloration.
- the yellow dye is also impaired which results in a shift of the coloration in the direction toward blue.
- the triarylmethane dye acid blue 9 is the most stable. However, it is also attacked if the test is continued and is discolored in the end.
- a complexing agent namely, ethylene-diaminetetraacetic acid tetrasodium salt
- a stabilizing agent instead of a buffer.
- the black stain in accordance with Example 2 went through four staining passes without a color change. A shift of the color tone toward blue-green was noted only after the fifth staining operation.
- This stain maintained its color consistency over at least five staining operations. Only after further staining operations could a color shift in the green direction (discoloration of the red dye) and, in the further course of the test, a coloration in the direction toward blue (discoloration of the yellow dye) be observed.
- Example 1 If the results of this test are compared with those of Example 1 and Example 2 it becomes clear that a further improvement in the stability of the stain can be achieved by the presence of a buffer, as well as a complexing agent. While, with sodium carbonate as the sole stabilizing agent, a color constancy over three to four staining operations was achieved and while, with ethylenediaminetetraacetic acid tetrasodium salt as a sole stabilizing agent, a color constancy over four staining operations, the color constancy of a stain wherein the buffer and the complexing agent are simultaneously present is further improved. This is shown by the fact that, in the test in accordance with Example 3, a color constancy over at least five staining operations was observed. Obviously, the buffer and the complexing agent complement each other in a synergistic way.
- Poplar and jelutong wood was dyed in this test.
- the green color of the stain was preserved without change over at least six staining passes.
- the stabilizing agents were omitted with the result that a discoloration toward blue could already be observed after one staining pass.
- the synergistic effect of the simultaneous presence of a buffer and a complexing agent became clear from this test result also.
- the food black 1 dye is a diazo dye.
- a mixture of ammonium carbonate (buffer) and 1,2-cyclohexylinedinitrilotetraacetic acid disodium salt (complexing agent) was added to the stain as a stabilizing agent. From the result it could be determined that the dark grey color of the stain remained stable over at least four staining operations.
- a comparison test without stabilizing agents showed that a discoloration in the direction toward green had appeared after only one staining pass which, with an increasing number of staining operations, was displaced more and more toward blue.
- Example 3 at least five staining operations, in Example 4 at least six staining operations
- Example 4 at least six staining operations
- This orange-colored stain retained its color constancy over at least five staining operations. Only after further staining operations was a color shift in the direction toward yellow observed and, during the further course of the test, a discoloration of the yellow dye too was observed. The synergistic effect of the simultaneous presence of the complexing agent and the buffer is noticeable here also.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
A wood stain which is water-based, which is suitable for staining wood, and which is comprised of water; at least one dye selected from the group consisting of azo, diazo and triarylmethane dyes; and a stabilizing agent which is effective to reduce free iron ion concentration in the stain when in contact with an autoclave composed of non-rust resistant steel during the staining process. The stabilizing agent includes at least one buffer effective to maintain the pH of the wood stain at greater than 7.0. Alternatively or additionally, the stabilizing agent includes at least one complexing agent which forms a complex with iron ions.
Description
This is a division of application Ser. No. 08/509,300 filed Jul. 31, 1995, now U.S. Pat. No. 5,567,206.
The present disclosure relates to the subject matter disclosed in German Application No. P 44 27 299.5 filed Aug. 2, 1994, the entire specification of which is incorporated herein by reference.
1. Field of the Invention
This invention relates to a water-based stain for staining wood containing at least one dye, such as azo, diazo and triarylmethane dyes, and to a method for staining wood. In particular, the present invention relates to use of a stabilizing agent which may be a buffer and/or a complexing agent and which is effective to reduce the concentration of free iron ions in the stain from contact with an autoclave composed of non-rust-resistant steel, and thereby reduce coloration impairment of the stain.
2. Background of the Related Art
Wood stains are known, for example, from the furniture industry and are used for staining the surface of a piece of furniture while preserving its natural grain if possible. For this purpose, the surfaces of the pieces of furniture are treated with the stain by, for example, painting or spraying, and any other method know in the art. In such treatment processes the stain penetrates the wood surface only slightly. However, this is often not sufficient for achieving the desired staining of the wood surface. There are also cases where not only a surface staining of the wood is desired, but staining that penetrates deeper into or even entirely through the wood. The latter is the case in connection with the manufacture of lead pencils and colored pencils wherein the body of wood enclosing the lead of the pencil is intended to have a continuously uniform coloration. A further example of applications where penetrating staining of wood is desired is for wood blanks which are intended to be worked later, for example, by cutting or sawing, without the plain, unstained wood appearing at the worked places.
Such staining processes are usually performed in autoclaves. For this purpose, small pieces of wood, e.g., wood blanks in the form of small boards in the case of lead pencil or colored pencil manufacture, are placed into an autoclave and dipped into a colored stain. Then the autoclave is closed and the staining or penetrating staining is started by means of temperature and pressure increases as is well known in the art. Depending on the type of wood and the thickness of the wood blanks to be stained, penetrating staining can take several hours or even several days.
The dyes used can naturally be from a very broad spectrum of different dye types. However, as a rule two groups of dyes are used for staining wood, namely, acid dyes, which are also called anionic dyes, and basic or cationic dyes.
While no problems worth mentioning regarding the stability of the stains occur in connection with any of the mentioned dye groups in autoclaves of rust-resistant steel, for example, V2A steel, it was noted that the dyes were increasingly impaired during continued treatment when acid dyes were used in autoclaves made of normal, i.e., not anti-corrosive steel. The impairment consists in an increasing change in the color of the added dye.
The color change effect occurs in particular with azo- and diazo-dyes, but in a weakened form, also with triarylmethane dyes. It is known that acid dyes are used in a neutral to alkaline environment. At the end of the dying process the pH value of the stain typically has been lowered to a varying degree into the acid range, depending on the type of wood used. The reason for this is that organic acids are contained in the wood which cause an increase in the H3 O+ ion concentration. However, this effect cannot be or at least cannot be totally responsible for the observed color changes, since generally no color changes were observed in connection with autoclaves of special steel in spite of the lowering of the pH values.
Based on the above mentioned observation, it is the object of the present invention to reduce or eliminate the prior art color change effect by providing a stain and a staining method for wood which can be used in autoclaves made of non-rust-resistant steel and while using azo, diazo and triarylmethane dyes.
This object is attained by the present invention which provides a wood stain which is water-based and which is suitable for staining wood, comprising: water; at least one dye selected from the group consisting of azo, diazo and triarylmethane dyes; and a stabilizing agent which is effective to reduce free iron ion concentration. The wood stain has a pH and the stabilizing agent comprises at least one buffer effective to maintain the pH of the wood stain at greater than 7.0. The at least one buffer may be at least one inorganic salt which is water-soluble. The stabilizing agent may alternatively or additionally comprise at least one complexing agent which forms a complex with iron ions. The wood stain may additionally comprise at least one auxiliary agent selected from the group consisting of wetting agents, water-soluble wax dispersions, water-soluble fatty acid derivatives, and preserving agents.
The present invention additionally provides a method for staining wood, comprising: placing the wood into an autoclave composed of non-rust-resistant steel; submerging the wood in a wood stain according to the invention; and staining the wood under pressure and temperature conditions effective therefor.
The present invention additionally contemplates reducing coloration impairment of dyes contained in wood stain during staining of wood in an autoclave composed of non-rust-resistant steel, the wood stain being comprised of water and at least one dye selected from the group consisting of azo, diazo and triarylmethane dyes, by incorporating into the wood stain a stabilizing agent according to the invention which is effective to reduce free iron ion concentration in the wood stain when in contact with the autoclave.
Thus, the stain of the invention contains a stabilizer which reduces the amount of iron from the autoclave which would otherwise solubilize as iron ions into the stain. It was surprisingly shown that, by means of this, the previously observed color changes no longer occur or occur only after considerably longer treatment periods. The concentration of the iron ions which move into the dye solution is reduced or kept small by the stabilization agent added in accordance with the invention and, therefore, the effect on the chromophoric groups of the dyes is reduced. The effect of the iron ions on the dye can be interpreted in such a way that the iron ions cooperate with the π-electron systems of the dye as does a Lewis acid and, in the process, changes its light adsorption properties. It therefore appears that the concentration of free iron ions plays a decisive role in the generation of the color change effect. In the neutral or alkaline environment usually present in the mentioned dye-containing stains these would overwhelmingly be Fe-III-ions.
In principle, there are two ways available to reduce the iron ion concentration or to prevent creation of a concentration of iron ions which affects the chromophoric group of the dyes.
The stabilizing agent may be a buffer substance which maintains the pH value of the stain at a level which is greater than 7.0. Then, little or no concentration of Fe-II and Fe-III ions can even be created in this pH range, since the iron ions are precipitated as iron hydroxide. The buffer, which preferably is a water-soluble inorganic salt, counteracts a lowering of the pH by organic acids present in the wood. Substances are advantageously employed as buffers which neither enter into an interaction with the wood to be dyed nor with the dye employed. Buffer substances such as acetates and carbonates of ammonium, potassium and sodium, as well as ammonium hydrogen phosphate, secondary and tertiary phosphates of potassium and sodium or ammonium sodium hydrogen phosphate should be mentioned here by way of example but not limitation. However, organic buffer substances can also be used, for example, sodium acetate.
The iron ions can also be made innocuous in that they may be masked with the aid of a complexing agent. The formation of a concentration of iron ions per se is not prevented by this, but they are no longer free ions, i.e., they are captured by the ligands of the complex-forming substance and are therefore shielded so to speak. Thus, their property as a Lewis acid in respect to the π electrons of the dye cannot be brought to bear. The following substances may be used as complexing agents and are given by way of example but not limitation: diacetyldioxime, 1,10-phenanthroline, terpyridine and water-soluble salts of ethylene-diaminetetraacetic acid, diethylenetriamine pentaacetic acid or 1,2-cyclohexylinedinitrilotetraacetic acid.
The stabilizing agent can also contain a buffer substance, as well as a complexing agent. It has been surprisingly shown that a stabilization of the stain, which exceeds the extent of the effects of the individual substances, was achieved by the simultaneous presence of a buffer and a complexing agent as will be discussed further in the following.
The stain in accordance with the invention can additionally contain the usual additives employed with such stains as is known in the staining art, such as wetting agents, water-soluble wax dispersions, fatty acid derivatives, and preserving agents, without interference with the effect in accordance with the invention. The addition of preserving agents, such as fungicides, is indicated, for example, if stained wood blanks are intended to be stored over extended periods of time under humid conditions, such as in the tropics. It is mainly their job to prevent the wood blanks from being affected by fungi. Water-soluble wax dispersions or water-soluble fatty acid derivatives are added, for example, if it is intended to produce pencils. The mentioned substances are deposited in the hollow or capillary spaces of the wood and make it possible to easily sharpen the pencil made therefrom in that the chips cut from the tip cone of the pencil do not break easily and crumble. The surface tension of the main constituent of the stain, water, is reduced by the addition of a wetting agent. The penetration ability of the stain into the capillary system of the wood is increased thereby.
A composition of the wood stain in accordance with the invention, in weight-%, comprises from about 1 to about 20% of at least one dye; from about 0.01 to about 5% of at least one wetting agent; from about 0.1 to about 0.5% of at least one preserving agent; from about 1 to about 20% of a stabilizing agent, and remainder water. Advantageous formulations for stains in accordance with the invention are given herein in the Examples which follow.
The invention will now be explained in detail by means of exemplary embodiments.
A laboratory autoclave with a capacity of approximately 5 liters was used for preparing the following exemplary formulations. The autoclave was made of ordinary steel, i.e., non-rust-resistant steel. Contact of the stain with the mentioned material was always the case. A volume of approximately 2 liters of wood in the form of small boards, such as are used in cosmetic, lead or colored pencil manufacture, was placed into the autoclave. The autoclave was filled with stain at least sufficiently for the wood pieces to be completely covered by the stain. The temperature in all cases was 50° C. to 60° C. The pH value fell to a level of between 8 and 10. Furthermore, pressure values between 13 and 15 bar were maintained.
The tests were performed in such a way that, respectively, at the end of a staining pass of approximately 24 hours, the test pieces were taken out and the coloration of the pieces and/or of the rest of the stain remaining in the autoclave was checked. Then fresh, i.e., unstained pieces were inserted and the stain used up in the previous staining process was replenished.
The percentages cited in the formulations below relate to weight-%. The dyes tested are identified as follows:
C.I. 19140 is C16 H9 N4 O9 S2 Na3 which is the trisodium salt of 5-hydrox-1-(4-sulfonatophenyl)-4-(4-sulfonatophenylazo)- pyrazole-3-carboxylic acid.
C.I. 16255 is C20 H11 N2 O10 S3 Na3 which is the trisodium salt of 7-hydroxy-8-(4-sulfonato-1-naphthylazo)-napthaline-1,3-disulfonic acid.
C.I. 42090 is C37 H34 N2 O9 S3 Na2 which is the disodium salt of α-{4-(N-ethyl-3-sulfonatobenzylamino)phenyl}-α-{4-(N-ethyl-3-sulfonatobenzylimino)-cyclohexa-2,5-dienylidene}-toluene-2-sulfenic acid.
C.I. 42051 is (C27 H31 N2 O7 S2)CA or C27 H31 N2 O7 S2 Na which is either the calcium salt or the sodium salt of 2,4-disulfo-5-hydroxy-4', 4"-bis-(diethylamino)-triphenyl-carbinolanhydride.
C.I. 28840 is C28 H27 N5 O14 S4 Na4 which is the tetrasodium salt of 4-acetamido-5-hydroxy-6-{7-sulfonato-4-(4-sulfonatophenylazo)-1-naphthylazo}naphtalene-1,7-disulfonic acid.
______________________________________
Reference Example without Stabilizing Agent (Black Stain):
______________________________________
Acid Yellow 23 C.I. 19140
0.8%,
Acid Red 18 C.I. 16255 2.8%,
Acid Blue 9 C.I. 42090 1.4%,
Polyoxyethylene- (20) -sorbitan-monolaurate
0.8%,
Mixture of chloroacetamide/sodium benzoate
0.2%,
and the remainder water.
______________________________________
Two different types of wood were stained, namely jelutong wood and wood of the California cedar. The volume of the respective wood type was approximately 1 liter. As a result it was noted that following the first staining pass the black coloration of the stain already showed a slightly greenish cast. A second staining process was then performed after the previously used up stain had been replenished. Following the second staining pass the black stain showed a distinct green coloration.
This test result shows that conventional stains are not practical for use in autoclaves of normal, non-rust-resistant steel, because only a single staining process can be performed. The stain is already damaged in the first treatment phase extending over 24 hours to such an extent that it is no longer usable for a second staining process. For performing wood staining on an industrial scale this means that a continuous operation, wherein a large stain volume remains in the autoclave during several staining processes and only fresh batches of wood are placed in the autoclave and used up stain is replenished, is not possible.
______________________________________
Acid Yellow 23 C.I. 19140
0.8%,
Acid Red 18 C.I. 16255 2.8%,
Acid Blue 9 C.I. 42090 1.4%,
Polyoxyethylene- (20) -sorbitan-monolaurate
0.8%,
Mixture of chloroacetamide/sodium benzoate
0.2%,
Sodium carbonate 2.5%,
and the remainder water.
______________________________________
It was possible to perform between three and four staining operations with the stain without the degree of blackening of the stain or the wood stained with it having changed. A color shift in the direction toward green was observed only after further staining passes and, in the further course of continuing the test, a color change in the direction of blue-green.
The two dyes used in the above two tests, acid red 18 and acid yellow 23, as well as in the following ones, are azo dyes, while acid blue 9 is a triarylmethane dye. These dyes belong to the group of acid or anionic dyes. As far as the effect on the color or the chromophorous groups of the dyes by the iron ions entering the dye solution from the autoclave is concerned, the test result in accordance with Example 1 can be interpreted as follows: the azo dyes, i.e., acid yellow 23 and especially acid red 18, are the most sensitive. They are impaired first. Thus, the red tones of the dye mixture are weakened first. The relative proportion of the blue and yellow dye accordingly increases, which results in the observed green coloration. With an increasing length of the test, the yellow dye is also impaired which results in a shift of the coloration in the direction toward blue. Thus, the triarylmethane dye acid blue 9 is the most stable. However, it is also attacked if the test is continued and is discolored in the end.
It can be clearly observed from a comparison between the Reference Example and Example 1 that a considerable extension of the staining time can be achieved by the addition of a buffer, in the present example, Example 1, sodium chloride. A complete refill of an autoclave with fresh stain need only be performed after three to four staining processes. If it is taken into consideration that, in operations on an industrial scale, considerably greater amounts of stain are used, the advantage of the stain in accordance with the invention and of the method in accordance with the invention over conventional staining processes becomes clear. The savings of time and material are evident.
______________________________________
Acid yellow 23 C.I. 19140
0.8%,
Acid Red 18 C.I. 16255 2.8%,
Acid Blue 9 C.I. 42090 1.4%,
Polyoxyethylene- (20) -sorbitan-monolaurate
0.8%,
Mixture of chloroacetamide/sodium benzoate
0.2%,
Ethylenediaminetetraacetic acid tetrasodium
3.0%,
salt
and the remainder water.
______________________________________
In this example, a complexing agent, namely, ethylene-diaminetetraacetic acid tetrasodium salt, was used as a stabilizing agent instead of a buffer. The black stain in accordance with Example 2 went through four staining passes without a color change. A shift of the color tone toward blue-green was noted only after the fifth staining operation. Here, too, the least stable dye, acid red 18, was first impaired.
______________________________________
Acid Blue 9 C.I. 42090 1.4%,
Acid Red 18 C.I. 16255 2.8%,
Acid Yellow 23 C.I. 19140
0.8%,
Polyoxyethylene- (20) -sorbitan-monolaurate
0.8%,
Mixture of chloroacetamide/sodium benzoate
0.2%,
Sodium acetate 3.0%,
Ethylenediaminetetraacetic acid tetrasodium
3.0%,
salt
and the remainder water.
______________________________________
This stain maintained its color consistency over at least five staining operations. Only after further staining operations could a color shift in the green direction (discoloration of the red dye) and, in the further course of the test, a coloration in the direction toward blue (discoloration of the yellow dye) be observed.
If the results of this test are compared with those of Example 1 and Example 2 it becomes clear that a further improvement in the stability of the stain can be achieved by the presence of a buffer, as well as a complexing agent. While, with sodium carbonate as the sole stabilizing agent, a color constancy over three to four staining operations was achieved and while, with ethylenediaminetetraacetic acid tetrasodium salt as a sole stabilizing agent, a color constancy over four staining operations, the color constancy of a stain wherein the buffer and the complexing agent are simultaneously present is further improved. This is shown by the fact that, in the test in accordance with Example 3, a color constancy over at least five staining operations was observed. Obviously, the buffer and the complexing agent complement each other in a synergistic way.
In a control test, sodium acetate (buffer) and ethylenediaminetetraacetic acid tetrasodium salt (complexing agent) were omitted. Discoloration in the green direction was already observed after only one staining operation.
______________________________________
Acid Blue 9 C.I. 42051 1.0%,
Acid Yellow 23 C.I. 19140
4.0%,
Polyoxyethylene- (20) -sorbitan-monolaurate
2.5%,
Polyglycolether 2.0%,
Paraben mixture 0.3%,
Dipotassium hydrogen phosphate
2.0%,
Ethylenediaminetetraacetic acid tetrasodium
4.0%,
salt
and the remainder water.
______________________________________
Poplar and jelutong wood was dyed in this test. The green color of the stain was preserved without change over at least six staining passes. In a comparative test, the stabilizing agents were omitted with the result that a discoloration toward blue could already be observed after one staining pass. The synergistic effect of the simultaneous presence of a buffer and a complexing agent became clear from this test result also.
______________________________________
Food Black 1 C.I. 28440 0.5%,
Acid Yellow 23 C.I. 19140
0.4%,
Acid Red 18 C.I. 16255 1.4%,
Acid Blue 9 C.I. 42090 0.7%,
Polyoxyethylene- (20) -sorbitan-monolaurate
0.5%,
Paraben mixture 0.3%,
Sodium stearate 3.0%,
Ammonium carbonate 2.0%,
1,2--cyclohexylinedinitrilotetraacetic acid
6.0%,
disodium salt
and the remainder water.
______________________________________
The food black 1 dye is a diazo dye. A mixture of ammonium carbonate (buffer) and 1,2-cyclohexylinedinitrilotetraacetic acid disodium salt (complexing agent) was added to the stain as a stabilizing agent. From the result it could be determined that the dark grey color of the stain remained stable over at least four staining operations. A comparison test without stabilizing agents showed that a discoloration in the direction toward green had appeared after only one staining pass which, with an increasing number of staining operations, was displaced more and more toward blue. That only four stain operations could be achieved in this example in spite of the presence of a buffer and a complexing agent (in Example 3 at least five staining operations, in Example 4 at least six staining operations) could perhaps be explained by the fact that the food black 1 C.I. 28440 diazo dye has an even lesser stability with respect to iron ions than acid red 18 C.I. 16255.
______________________________________
Acid Red 18 C.I. 16255 3.6%,
Acid Yellow 23 C.I. 19140
1.4%,
Polyoxyethylene- (20) -sorbitan-monolaurate
0.1%,
Chloroacetamide/sodium benzoate mixture
0.2%,
Sodium acetate 3.0%,
Diacetyldioxime 4.0%,
and the remainder water.
______________________________________
This orange-colored stain retained its color constancy over at least five staining operations. Only after further staining operations was a color shift in the direction toward yellow observed and, during the further course of the test, a discoloration of the yellow dye too was observed. The synergistic effect of the simultaneous presence of the complexing agent and the buffer is noticeable here also.
In conclusion it should be noted that color impairment was observed also with other than the above mentioned dye groups if the staining process was performed in autoclaves made of non-rust-resistant steel. It can therefore be assumed with some justification that impairment of these additional dyes was also a result of the presence of free iron ions.
It should be possible to transfer the principle on which the instant invention is based, namely, the reduction of the iron ion concentration by means of buffers and/or complexing agents, in general to dyes of all types which are impaired in their coloration by contact with the surface of an autoclave made of non-rust-resistant steel.
It is understood that various other modifications will be apparent to, and can be readily made by, those skilled in the art without departing from the scope and spirit of the present invention. Accordingly, it is not intended that the scope of the claims appended hereto be limited to the description set forth above but, rather, that the claims be construed as encompassing all of the features of patentable novelty which reside in the present invention including all features which would be treated as equivalents thereof by those skilled in the art to which the invention pertains.
Claims (14)
1. A wood stain which is water-based and which is suitable for staining wood, comprising:
from about 1-20% of at least one dye substance selected from the group consisting of azo, diazo, and triarylmethane dyes and mixtures thereof;
from about 0.01 to about 5% of at least one wetting agent;
from about 0.1% to about 0.5% of at least one preserving agent; and
from about 1 to about 20% of a stabilizing agent which is effective to reduce free iron ion concentration, which comprises one of (a) at least one buffer effective to maintain pH of the wood stain at greater than 7, (b) at least one complexing agent which forms a complex with iron ions, or (c) a mixture of the at least one buffer and the at least one complexing agent; and
remainder water,
wherein the buffer is selected from the group consisting of acetates and carbonates of ammonium, potassium and sodium; ammonium hydrogen phosphate; secondary and tertiary phosphates of potassium and sodium; and ammonium sodium hydrogen phosphate, and
wherein the complexing agent is selected from the group consisting of diacetyldioxime; 1,10- phenanthroline; terpyridine; water-soluble salts of ethylene-diamine-tetraacetic acid; diethylenetriamine pentaacetic acid; 1,2-cyclohexylinedinitrilotetraacetic acid, and mixtures thereof.
2. The wood stain in accordance with claim 1, wherein the wood stain has a pH, and wherein the stabilizing agent comprises a mixture of the at least one buffer effective to maintain the pH of the wood stain at greater than 7.0 and the at least one complexing agent which forms a complex with iron ions.
3. The wood stain in accordance with claim 1, further comprising at least one auxiliary agent selected from the group consisting of water-soluble wax dispersions and water-soluble fatty acid derivatives.
4. A wood stain which is water-based, which is suitable for staining wood, and which has a composition in weight-%, comprising:
0.8% of Acid Yellow 23 C.I. 19140;
2.8% of Acid Red 18 C.I. 16255; and
1.4% of Acid Blue 9 C.I. 42090 as dye substance;
0.8% of a wetting agent comprised of polyoxyethylene-(20)-sorbitan-monolaurate;
0.2% of a preservative comprised of a mixture of chloroacetamide and sodium benzoate;
2.5% of a stabilizing agent comprised of sodium carbonate; and
remainder water.
5. A wood stain which is water-based, which is suitable for staining wood, and which has a composition in weight-%, comprising:
0.8% of Acid Yellow 23 C.I. 19140;
2.8% of Acid Red 18 C.I. 16255; and
1.4% of Acid Blue 9 C.I. 42090 as dye substance;
0.8% of a wetting agent comprised of polyoxyethylene-(20)-sorbitan-monolaurate;
0.2% of preservative comprised of a mixture of chloroacetamide and sodium benzoate;
3.0% of complexing agent comprised of ethylenediaminetetraacetic acid tetrasodium salt; and
remainder water.
6. A wood stain which is water-based, which is suitable for staining wood, and which has a composition in weight-% comprising:
3.6% of Acid Red 18 C.I. 16255; and
1.4% of Acid Yellow 23 C.I. 19140 as dye substance;
0.1% of wetting agent comprised of polyoxyethylene-(20)-sorbitan-monolaurate;
0. 2% of preservative comprised of a mixture of chloroacetamide and sodium benzoate;
3.0% of stabilizing agent comprised of sodium acetate;
4.0% of complexing agent comprised of diacetyldioxime; and
remainder water.
7. A wood stain which is water-based, which is suitable for staining wood, and which has a composition in weight-%, comprising:
1.0% of Acid Blue 9 C.I. 42051; and
4.0% of Acid Yellow 23 C.I. 19140 as dye substance;
2.5% of wetting agent comprised of polyoxyethylene-(20)-sorbitan-monolaurate;
2.0% of polyglycolether;
0.3% of preservative comprised of paraben mixture;
2.0% of stabilizing agent comprised of dipotassium hydrogen phosphate;
4.0% of complexing agent comprised of ethylenediaminetetraacetic acid tetrasodium salt; and
remainder water.
8. A wood stain which is water-based, which is suitable for staining wood, and which has a composition in weight-%, comprising:
0.5% of Food Black 1 C.I. 28440;
0.4% of Acid Yellow 23 C.I. 19140;
1.4% of Acid Red 18 C.I. 16255; and
0.7% of Acid Blue 9 C.I. 42090 as dye substance;
0.5% of wetting agent comprised of polyoxyethylene-(20)-sorbitan-monolaurate;
0.3% of preservative comprised of paraben mixture;
3.0% of sodium stearate;
2.0% of stabilizing agent comprised of ammonium carbonate;
6.0% of complexing agent comprised of 1,2-cyclohexylinedinitrilotetraacetic acid disodium salt; and
remainder water.
9. A wood stain which is water-based and which is suitable for staining wood, comprising:
from about 1-20% of at least one dye substance selected from the group consisting of Acid Yellow 23 C.I. 19140, Acid Red 18 C.I.16255, Acid Blue 9 C.I. 42090, and mixtures thereof;
from about 0.01 to about 5% of at least one wetting agent;
from about 0.1% to about 0.5% of at least one preserving agent; and
from about 1 to about 20% of a stabilizing agent which is effective to reduce free iron ion concentration, which comprises one of (a) at least one buffer effective to maintain the pH of the wood stain at greater than 7, (b) at least one complexing agent which forms a complex with iron ions, or (c) a mixture of the at least one buffer and the at least one complexing agent; and
remainder water,
wherein the buffer is selected from the group consisting of acetates and carbonates of ammonium, potassium and sodium; ammonium hydrogen phosphate; secondary and tertiary phosphates of potassium and sodium; and ammonium sodium hydrogen phosphate, and
wherein the complexing agent is selected from the group consisting of diacetyldioxime; 1,10- phenanthroline; terpyridine; water-soluble salts of ethylene-diamine-tetraacetic acid; diethylenetriamine pentaacetic acid; 1,2-cyclohexylinedinitrilotetraacetic acid, and mixtures thereof.
10. The wood stain in accordance with claim 9, wherein the wood stain has a pH, and wherein the stabilizing agent comprises at least one buffer effective to maintain the Ph of the wood stain at greater than 7.0.
11. The wood stain in accordance with claim 9, wherein the stabilizing agent comprises at least one complexing agent which forms a complex with iron ions.
12. The wood stain in accordance with claim 9, wherein the wood stain has a pH, and wherein the stabilizing agent comprises at least one buffer effective to maintain the Ph of the wood stain at greater than 7.0 and at least one complexing agent which forms a complex with iron ions.
13. The wood stain in accordance with claim 9, further comprising at least one auxiliary agent selected from the group consisting of water-soluble wax dispersions and water-soluble fatty acid derivatives.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/652,309 US5746778A (en) | 1994-08-02 | 1996-05-23 | Wood stain containing a stabilizing agent |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4427299.5 | 1994-08-02 | ||
| DE4427299A DE4427299A1 (en) | 1994-08-02 | 1994-08-02 | Stain and method of coloring wood |
| US08/509,300 US5567206A (en) | 1994-08-02 | 1995-07-31 | Stain and method for staining wood |
| US08/652,309 US5746778A (en) | 1994-08-02 | 1996-05-23 | Wood stain containing a stabilizing agent |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US08/509,300 Division US5567206A (en) | 1994-08-02 | 1995-07-31 | Stain and method for staining wood |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US5746778A true US5746778A (en) | 1998-05-05 |
Family
ID=6524707
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US08/509,300 Expired - Fee Related US5567206A (en) | 1994-08-02 | 1995-07-31 | Stain and method for staining wood |
| US08/652,309 Expired - Fee Related US5746778A (en) | 1994-08-02 | 1996-05-23 | Wood stain containing a stabilizing agent |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US08/509,300 Expired - Fee Related US5567206A (en) | 1994-08-02 | 1995-07-31 | Stain and method for staining wood |
Country Status (5)
| Country | Link |
|---|---|
| US (2) | US5567206A (en) |
| EP (1) | EP0695608A1 (en) |
| JP (1) | JPH08188736A (en) |
| BR (1) | BR9503523A (en) |
| DE (1) | DE4427299A1 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6509145B1 (en) | 1998-09-30 | 2003-01-21 | Medtronic, Inc. | Process for reducing mineralization of tissue used in transplantation |
| US20030118981A1 (en) * | 2001-03-30 | 2003-06-26 | Torrianni Mark W. | Process for reducing mineralization of tissue used in transplantation |
| US6630002B2 (en) * | 2000-05-11 | 2003-10-07 | Ciba Specialty Chemicals Corporation | Process for the staining of wood with aqueous wood stains |
| US6645257B1 (en) * | 1999-10-06 | 2003-11-11 | Ciba Specialty Chemicals Corporation | Process for pigmenting wood |
| US6737094B2 (en) | 2000-05-31 | 2004-05-18 | Pepsico, Inc. | Low-staining orange food coloring composition |
| US20050119736A1 (en) * | 2003-10-30 | 2005-06-02 | Peter Zilla | Bioprosthetic tissue preparation with synthetic hydrogels |
| US20050266390A1 (en) * | 2004-06-01 | 2005-12-01 | Yuichiro Ueda | Processes for removing cells and cell debris from tissue and tissue constructs used in transplantation and tissue reconstruction |
| JP2013512968A (en) * | 2009-12-08 | 2013-04-18 | バンダービルト ユニバーシティ | Improved methods and compositions for venectomy and autotransplantation |
| US10190013B2 (en) | 2008-12-18 | 2019-01-29 | Axalta Coating Systems Ip Co., Llc | Stain composition |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19640873C2 (en) * | 1996-10-04 | 2001-04-19 | Staedtler Fa J S | Use of an aqueous surfactant emulsion or dispersion to improve the mechanical workability of wood |
| EP1093495B1 (en) | 1998-06-26 | 2004-03-17 | Binney & Smith Inc. | Erasable colored pencil lead |
| US6011084A (en) | 1998-06-26 | 2000-01-04 | Binney & Smith Inc. | Erasable colored pencil lead |
| US20060086283A1 (en) * | 2004-10-21 | 2006-04-27 | Premier Wood Treating, L.L.C. | Water repellent cellulose preservative |
| US20090288737A1 (en) * | 2008-05-23 | 2009-11-26 | Gilmet Mathew A | Apparatus for positioning and splitting wood |
| KR101286361B1 (en) * | 2011-06-22 | 2013-07-15 | 서종수 | Wood dyeing method using vacuum and dyeing wood |
| US10427318B1 (en) * | 2018-08-22 | 2019-10-01 | Roxann Groff | Method of creating a wood-based false stone |
| CN113561278A (en) * | 2021-07-16 | 2021-10-29 | 鼎峰工贸(高唐)有限公司 | Method for changing wood color permeability |
| CN115816577B (en) * | 2022-12-22 | 2025-08-26 | 广西壮族自治区林业科学研究院 | A method for controlling the color of high-performance reconstituted wood |
| CN117091925B (en) * | 2023-08-24 | 2024-07-19 | 福州迈新生物技术开发有限公司 | Dewaxing supplementing liquid suitable for universal system full-automatic immunohistochemical staining instrument and preparation method and application thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1360818A (en) * | 1971-11-16 | 1974-07-24 | Universal Oil Prod Co | Colouring solution and use thereof |
| JPS54126703A (en) * | 1978-03-22 | 1979-10-02 | Dantani Plywood Co | Wood dyeing method |
| DE3105642A1 (en) * | 1981-02-17 | 1982-08-19 | Remmers Chemie GmbH & Co, 4573 Löningen | Coloured wood preservatives which produce light- and weather-resistant colourings on wood and use thereof |
| US4348204A (en) * | 1979-01-19 | 1982-09-07 | Cassella Aktiengesellschaft | Aqueous dyestuff formulation, a process for its preparation and its use for dyeing and printing |
| US4715969A (en) * | 1984-12-24 | 1987-12-29 | Colgate Palmolive Co. | Controlling viscosity of fabric softening heavy duty liquid detergent containing bentonite |
| US4743268A (en) * | 1986-05-05 | 1988-05-10 | Westvaco Corporation | Dispersant composition for azo dyestuffs contaminated with soluble copper impurities |
| WO1991002033A1 (en) * | 1989-08-11 | 1991-02-21 | Universal Foods Corporation | Stable, fluid, aqueous pigment dispersions |
| US5171328A (en) * | 1990-10-04 | 1992-12-15 | Basf Aktiengesellschaft | Stabilizer-containing wood stains |
| DE4137851A1 (en) * | 1991-11-16 | 1993-05-19 | Basf Ag | METHOD FOR ADDING WOODEN FORMATION |
| DE4237063A1 (en) * | 1992-11-03 | 1994-05-05 | Faber Castell A W | Stain for the black coloring of wood |
| US5536761A (en) * | 1992-12-07 | 1996-07-16 | Sakura Color Products Corporation | Water base dye ink composition |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57123010A (en) * | 1981-01-24 | 1982-07-31 | Matsushita Electric Works Ltd | Method of preventing discoloration of wood |
| JPS62173205A (en) * | 1986-01-27 | 1987-07-30 | 松下電工株式会社 | Manufacture of colored decorative veneer |
-
1994
- 1994-08-02 DE DE4427299A patent/DE4427299A1/en not_active Withdrawn
-
1995
- 1995-07-15 EP EP95111141A patent/EP0695608A1/en not_active Ceased
- 1995-07-31 US US08/509,300 patent/US5567206A/en not_active Expired - Fee Related
- 1995-08-01 JP JP7196832A patent/JPH08188736A/en active Pending
- 1995-08-02 BR BR9503523A patent/BR9503523A/en not_active Application Discontinuation
-
1996
- 1996-05-23 US US08/652,309 patent/US5746778A/en not_active Expired - Fee Related
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1360818A (en) * | 1971-11-16 | 1974-07-24 | Universal Oil Prod Co | Colouring solution and use thereof |
| JPS54126703A (en) * | 1978-03-22 | 1979-10-02 | Dantani Plywood Co | Wood dyeing method |
| US4348204A (en) * | 1979-01-19 | 1982-09-07 | Cassella Aktiengesellschaft | Aqueous dyestuff formulation, a process for its preparation and its use for dyeing and printing |
| DE3105642A1 (en) * | 1981-02-17 | 1982-08-19 | Remmers Chemie GmbH & Co, 4573 Löningen | Coloured wood preservatives which produce light- and weather-resistant colourings on wood and use thereof |
| US4715969A (en) * | 1984-12-24 | 1987-12-29 | Colgate Palmolive Co. | Controlling viscosity of fabric softening heavy duty liquid detergent containing bentonite |
| US4743268A (en) * | 1986-05-05 | 1988-05-10 | Westvaco Corporation | Dispersant composition for azo dyestuffs contaminated with soluble copper impurities |
| WO1991002033A1 (en) * | 1989-08-11 | 1991-02-21 | Universal Foods Corporation | Stable, fluid, aqueous pigment dispersions |
| US5171328A (en) * | 1990-10-04 | 1992-12-15 | Basf Aktiengesellschaft | Stabilizer-containing wood stains |
| DE4137851A1 (en) * | 1991-11-16 | 1993-05-19 | Basf Ag | METHOD FOR ADDING WOODEN FORMATION |
| DE4237063A1 (en) * | 1992-11-03 | 1994-05-05 | Faber Castell A W | Stain for the black coloring of wood |
| US5536761A (en) * | 1992-12-07 | 1996-07-16 | Sakura Color Products Corporation | Water base dye ink composition |
Non-Patent Citations (2)
| Title |
|---|
| Matsushita Electric Works, JP 57 123 010, Jul. 31, 1982, Database WPI, Section Ch, Week 8236, Derwent Publications, Abstract only. * |
| Matsushita Electric Works, JP 62 173 205, Jul. 30, 1987, Database WPI, Section Ch, Week 8736, Derwent Publications, Ltd., Abstract only. * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6509145B1 (en) | 1998-09-30 | 2003-01-21 | Medtronic, Inc. | Process for reducing mineralization of tissue used in transplantation |
| US6645257B1 (en) * | 1999-10-06 | 2003-11-11 | Ciba Specialty Chemicals Corporation | Process for pigmenting wood |
| US6630002B2 (en) * | 2000-05-11 | 2003-10-07 | Ciba Specialty Chemicals Corporation | Process for the staining of wood with aqueous wood stains |
| US6737094B2 (en) | 2000-05-31 | 2004-05-18 | Pepsico, Inc. | Low-staining orange food coloring composition |
| US7078163B2 (en) | 2001-03-30 | 2006-07-18 | Medtronic, Inc. | Process for reducing mineralization of tissue used in transplantation |
| US20030118981A1 (en) * | 2001-03-30 | 2003-06-26 | Torrianni Mark W. | Process for reducing mineralization of tissue used in transplantation |
| US20050119736A1 (en) * | 2003-10-30 | 2005-06-02 | Peter Zilla | Bioprosthetic tissue preparation with synthetic hydrogels |
| US20050266390A1 (en) * | 2004-06-01 | 2005-12-01 | Yuichiro Ueda | Processes for removing cells and cell debris from tissue and tissue constructs used in transplantation and tissue reconstruction |
| US20070123700A1 (en) * | 2004-06-01 | 2007-05-31 | Yuichiro Ueda | Processes for removing cells and cell debris from tissue and tissue constructs used in transplantation and tissue reconstruction |
| US10190013B2 (en) | 2008-12-18 | 2019-01-29 | Axalta Coating Systems Ip Co., Llc | Stain composition |
| JP2013512968A (en) * | 2009-12-08 | 2013-04-18 | バンダービルト ユニバーシティ | Improved methods and compositions for venectomy and autotransplantation |
| EP2509609B1 (en) * | 2009-12-08 | 2014-10-01 | Vanderbilt University | Improved methods and compositions for vein harvest and autografting |
| US10149470B2 (en) | 2009-12-08 | 2018-12-11 | Vanderbilt University | Methods and compositions for vein harvest and autografting |
| US10531654B2 (en) | 2009-12-08 | 2020-01-14 | Vanderbilt University | Methods and compositions for vein harvest and autografting |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0695608A1 (en) | 1996-02-07 |
| BR9503523A (en) | 1996-04-16 |
| DE4427299A1 (en) | 1996-02-08 |
| JPH08188736A (en) | 1996-07-23 |
| US5567206A (en) | 1996-10-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5746778A (en) | Wood stain containing a stabilizing agent | |
| CA1146704A (en) | Wood treatment composition | |
| US5364461A (en) | Inks used in multi-color printing | |
| DE69201931T2 (en) | Reduces run-off through the use of zwitterionic surfactants and cationic dyes. | |
| US4447336A (en) | Stabilized galactomannan gum compositions | |
| EP0305747B1 (en) | Process and composition for providing reduced discoloration of pyrithiones | |
| US4404181A (en) | Extended-life tissue fixative composition and method of using the same | |
| CA2124336A1 (en) | Antimicrobial dentifrice | |
| CA2055061A1 (en) | Cooling water treatment composition | |
| US5486231A (en) | Water repellent solution for wood and method | |
| US4400298A (en) | Wood preservative compositions | |
| DE2910403A1 (en) | BLEACHING AGENT | |
| JPS6295292A (en) | Dampening agent for offset printing | |
| CA2214761C (en) | Wood preservative | |
| DE2039242A1 (en) | Indicator for the detection of copper ions | |
| DE60217491T2 (en) | PRESERVATION OF WOOD WITH CALIUM FORMAT OR CALCIUM FORMAT | |
| US4950329A (en) | Wood preservative composition and method of treating wood with same | |
| EP0032653A2 (en) | Chemically correctable ink | |
| WO1996023635A1 (en) | Diffusible wood preservatives | |
| DE4237063C2 (en) | Stains and processes for blackening wood | |
| JP2002218940A (en) | Discoloration-preventing agent for astaxanthin pigment- containing food and method for preventing discoloration | |
| US5013747A (en) | Water-soluble antiseptic or antifungal composition | |
| US5009937A (en) | Sapstain control composition and method | |
| US4430091A (en) | Oxidation base dye composition and method of dyeing therewith | |
| GB2187096A (en) | Preservative for wood |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FEPP | Fee payment procedure |
Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
| FPAY | Fee payment |
Year of fee payment: 4 |
|
| REMI | Maintenance fee reminder mailed | ||
| LAPS | Lapse for failure to pay maintenance fees | ||
| LAPS | Lapse for failure to pay maintenance fees |
Free format text: PATENT EXPIRED FOR FAILURE TO PAY MAINTENANCE FEES (ORIGINAL EVENT CODE: EXP.); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
| STCH | Information on status: patent discontinuation |
Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362 |
|
| FP | Lapsed due to failure to pay maintenance fee |
Effective date: 20060505 |